# Supplementary Material (ESI) for Organic & Biomolecular Chemistry
# This journal is (c) The Royal Society of Chemistry 2009



data_global
_journal_name_full               Org.Biomol.Chem.

_journal_coden_Cambridge         0177

_publ_contact_author_name        'Philip Chan'
_publ_contact_author_email       WAIHONG@NTU.EDU.SG

_publ_section_title              
;
Iron(III) Chloride-Catalysed Direct Nucleophilic a-Substitution
of Morita-Baylis-Hillman Alcohols with Alcohols, Arenes, 1,3-Dicarbonyl
Compounds, and Thiols
;
loop_
_publ_author_name
'Philip Chan'
'Sally Chan'
'Xiaoxiang Zhang'

# Attachment 'chan29.cif'

data_chan29
_database_code_depnum_ccdc_archive 'CCDC 711037'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_absolute_configuration ad
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C27 H21 Cl O3'
_chemical_formula_sum            'C27 H21 Cl O3'
_chemical_formula_weight         428.89

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Orthorhombic
_symmetry_space_group_name_H-M   Pna2(1)

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, z+1/2'
'x+1/2, -y+1/2, z'
'-x+1/2, y+1/2, z+1/2'

_cell_length_a                   11.0930(5)
_cell_length_b                   13.4335(5)
_cell_length_c                   14.4720(6)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     2156.59(15)
_cell_formula_units_Z            4
_cell_measurement_temperature    173(2)
_cell_measurement_reflns_used    6322
_cell_measurement_theta_min      2.38
_cell_measurement_theta_max      31.09

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.29
_exptl_crystal_size_min          0.28
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.321
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             896
_exptl_absorpt_coefficient_mu    0.204
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.9414
_exptl_absorpt_correction_T_max  0.9451
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      173(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            35079
_diffrn_reflns_av_R_equivalents  0.0300
_diffrn_reflns_av_sigmaI/netI    0.0246
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_theta_min         2.07
_diffrn_reflns_theta_max         31.31
_reflns_number_total             6767
_reflns_number_gt                6067
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[\s^2^(Fo^2^)+(0.0621P)^2^+0.1012P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.01(4)
_refine_ls_number_reflns         6767
_refine_ls_number_parameters     280
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0424
_refine_ls_R_factor_gt           0.0351
_refine_ls_wR_factor_ref         0.1006
_refine_ls_wR_factor_gt          0.0917
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_restrained_S_all      1.073
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 0.73912(11) 0.20776(10) 0.05399(10) 0.0254(3) Uani 1 1 d . . .
H1 H 0.6774 0.2247 0.0967 0.031 Uiso 1 1 calc R . .
C2 C 0.71412(13) 0.20802(11) -0.03995(11) 0.0300(3) Uani 1 1 d . . .
H2 H 0.6359 0.2251 -0.0614 0.036 Uiso 1 1 calc R . .
C3 C 0.80414(14) 0.18311(10) -0.10212(11) 0.0303(3) Uani 1 1 d . . .
C4 C 0.91693(14) 0.15493(11) -0.07201(11) 0.0322(3) Uani 1 1 d . . .
H4 H 0.9770 0.1352 -0.1150 0.039 Uiso 1 1 calc R . .
C5 C 0.94161(12) 0.15572(11) 0.02235(10) 0.0270(3) Uani 1 1 d . . .
H5 H 1.0197 0.1374 0.0433 0.032 Uiso 1 1 calc R . .
C6 C 0.85391(10) 0.18288(8) 0.08670(9) 0.0200(2) Uani 1 1 d . . .
C7 C 0.88262(10) 0.18165(9) 0.18958(9) 0.0187(2) Uani 1 1 d . . .
H7 H 0.9722 0.1774 0.1958 0.022 Uiso 1 1 calc R . .
C8 C 0.84267(10) 0.27533(8) 0.23873(9) 0.0187(2) Uani 1 1 d . . .
C9 C 0.73615(11) 0.29953(9) 0.27735(11) 0.0237(2) Uani 1 1 d . . .
H9 H 0.6690 0.2557 0.2786 0.028 Uiso 1 1 calc R . .
C10 C 0.73339(11) 0.40201(10) 0.31822(10) 0.0248(3) Uani 1 1 d . . .
H10A H 0.7104 0.3998 0.3843 0.030 Uiso 1 1 calc R . .
H10B H 0.6758 0.4452 0.2847 0.030 Uiso 1 1 calc R . .
C11 C 0.86274(11) 0.43938(10) 0.30654(11) 0.0258(3) Uani 1 1 d . . .
H11A H 0.8640 0.5036 0.2730 0.031 Uiso 1 1 calc R . .
H11B H 0.9018 0.4486 0.3674 0.031 Uiso 1 1 calc R . .
C12 C 0.92628(10) 0.35963(9) 0.25160(9) 0.0196(2) Uani 1 1 d . . .
C13 C 0.82921(10) 0.08750(8) 0.23469(9) 0.0182(2) Uani 1 1 d . . .
H13 H 0.7394 0.0877 0.2284 0.022 Uiso 1 1 calc R . .
C14 C 0.88244(11) -0.00496(9) 0.18645(9) 0.0210(2) Uani 1 1 d . . .
C15 C 0.80400(11) -0.07424(9) 0.13292(9) 0.0215(2) Uani 1 1 d . . .
C16 C 0.68295(12) -0.05516(10) 0.11367(10) 0.0265(3) Uani 1 1 d . . .
H16 H 0.6464 0.0043 0.1356 0.032 Uiso 1 1 calc R . .
C17 C 0.61570(13) -0.12301(11) 0.06246(11) 0.0324(3) Uani 1 1 d . . .
H17 H 0.5336 -0.1093 0.0488 0.039 Uiso 1 1 calc R . .
C18 C 0.66803(15) -0.21041(12) 0.03139(11) 0.0344(3) Uani 1 1 d . . .
H18 H 0.6215 -0.2571 -0.0027 0.041 Uiso 1 1 calc R . .
C19 C 0.78838(15) -0.22977(12) 0.05005(13) 0.0364(3) Uani 1 1 d . . .
H19 H 0.8243 -0.2895 0.0282 0.044 Uiso 1 1 calc R . .
C20 C 0.85643(12) -0.16253(10) 0.10040(11) 0.0286(3) Uani 1 1 d . . .
H20 H 0.9388 -0.1762 0.1129 0.034 Uiso 1 1 calc R . .
C21 C 0.86433(10) 0.08218(9) 0.33692(9) 0.0217(2) Uani 1 1 d . . .
C22 C 0.78488(11) 0.02585(9) 0.40137(10) 0.0238(2) Uani 1 1 d . . .
C23 C 0.67891(13) -0.02104(11) 0.37194(11) 0.0318(3) Uani 1 1 d . . .
H23 H 0.6580 -0.0214 0.3083 0.038 Uiso 1 1 calc R . .
C24 C 0.60432(14) -0.06705(12) 0.43624(13) 0.0398(4) Uani 1 1 d . . .
H24 H 0.5325 -0.0991 0.4164 0.048 Uiso 1 1 calc R . .
C25 C 0.63398(18) -0.06645(13) 0.52840(13) 0.0457(5) Uani 1 1 d . . .
H25 H 0.5815 -0.0966 0.5721 0.055 Uiso 1 1 calc R . .
C26 C 0.73957(19) -0.02236(14) 0.55806(12) 0.0454(4) Uani 1 1 d . . .
H26 H 0.7601 -0.0233 0.6218 0.055 Uiso 1 1 calc R . .
C27 C 0.81577(16) 0.02336(11) 0.49492(11) 0.0335(3) Uani 1 1 d . . .
H27 H 0.8889 0.0529 0.5153 0.040 Uiso 1 1 calc R . .
Cl1 Cl 0.77506(4) 0.19108(3) -0.21995(3) 0.04467(11) Uani 1 1 d . . .
O1 O 1.02929(8) 0.36352(7) 0.22208(7) 0.0264(2) Uani 1 1 d . . .
O2 O 0.99006(9) -0.01922(8) 0.19204(9) 0.0336(2) Uani 1 1 d . . .
O3 O 0.95432(9) 0.12431(8) 0.36443(7) 0.0321(2) Uani 1 1 d . . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
C1 0.0214(5) 0.0299(6) 0.0250(7) -0.0001(5) 0.0012(5) -0.0007(4)
C2 0.0284(6) 0.0338(7) 0.0278(7) 0.0010(6) -0.0049(5) -0.0019(5)
C3 0.0432(8) 0.0253(6) 0.0224(7) 0.0019(5) -0.0003(6) -0.0050(5)
C4 0.0361(7) 0.0333(7) 0.0271(7) -0.0012(5) 0.0088(5) 0.0006(6)
C5 0.0248(6) 0.0288(6) 0.0273(7) -0.0006(5) 0.0048(5) 0.0022(5)
C6 0.0206(5) 0.0181(5) 0.0213(6) 0.0007(4) 0.0017(4) -0.0017(4)
C7 0.0155(4) 0.0183(5) 0.0222(6) 0.0002(4) 0.0016(4) -0.0011(4)
C8 0.0166(4) 0.0181(5) 0.0214(6) -0.0003(4) -0.0006(4) -0.0013(4)
C9 0.0185(5) 0.0242(5) 0.0285(6) -0.0023(5) 0.0012(5) -0.0020(4)
C10 0.0209(5) 0.0241(6) 0.0294(7) -0.0039(5) 0.0000(5) 0.0026(4)
C11 0.0232(5) 0.0218(5) 0.0324(7) -0.0042(5) -0.0017(5) -0.0021(4)
C12 0.0184(4) 0.0192(5) 0.0212(5) 0.0030(4) -0.0040(4) -0.0014(4)
C13 0.0168(4) 0.0180(5) 0.0199(6) -0.0003(4) 0.0001(4) 0.0002(4)
C14 0.0214(5) 0.0191(5) 0.0226(6) 0.0005(4) 0.0006(4) 0.0010(4)
C15 0.0243(5) 0.0189(5) 0.0213(6) 0.0002(4) 0.0018(4) -0.0008(4)
C16 0.0249(5) 0.0236(6) 0.0311(7) -0.0051(5) -0.0026(5) 0.0001(4)
C17 0.0307(6) 0.0316(7) 0.0349(8) -0.0047(6) -0.0066(6) -0.0037(5)
C18 0.0426(8) 0.0286(7) 0.0320(8) -0.0075(6) -0.0001(6) -0.0106(6)
C19 0.0460(8) 0.0241(7) 0.0391(9) -0.0099(6) 0.0069(7) -0.0014(6)
C20 0.0289(6) 0.0232(6) 0.0335(8) -0.0046(5) 0.0036(5) 0.0010(5)
C21 0.0221(5) 0.0223(5) 0.0208(6) -0.0010(4) -0.0006(4) 0.0038(4)
C22 0.0276(6) 0.0216(5) 0.0223(6) 0.0036(5) 0.0027(5) 0.0068(4)
C23 0.0282(6) 0.0364(7) 0.0308(8) 0.0118(6) 0.0017(5) -0.0016(5)
C24 0.0307(7) 0.0402(8) 0.0485(10) 0.0224(7) 0.0091(7) 0.0036(6)
C25 0.0550(10) 0.0394(9) 0.0427(10) 0.0235(7) 0.0224(8) 0.0173(7)
C26 0.0721(12) 0.0391(9) 0.0251(8) 0.0117(7) 0.0093(8) 0.0169(8)
C27 0.0474(8) 0.0284(7) 0.0246(7) 0.0026(5) -0.0013(6) 0.0101(6)
Cl1 0.0670(3) 0.0446(2) 0.02236(17) 0.00243(16) -0.00500(18) -0.00664(18)
O1 0.0178(4) 0.0257(4) 0.0358(6) 0.0032(4) 0.0009(3) -0.0036(3)
O2 0.0220(4) 0.0319(5) 0.0469(7) -0.0105(4) -0.0042(4) 0.0057(4)
O3 0.0266(4) 0.0414(6) 0.0283(5) -0.0018(4) -0.0068(4) -0.0044(4)

_geom_special_details            
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C1 C2 1.387(2) . ?
C1 C6 1.3990(17) . ?
C2 C3 1.385(2) . ?
C3 C4 1.378(2) . ?
C3 Cl1 1.7388(16) . ?
C4 C5 1.393(2) . ?
C5 C6 1.3953(18) . ?
C6 C7 1.5227(18) . ?
C7 C8 1.5119(17) . ?
C7 C13 1.5417(16) . ?
C8 C9 1.3469(17) . ?
C8 C12 1.4756(16) . ?
C9 C10 1.4988(18) . ?
C10 C11 1.5296(17) . ?
C11 C12 1.5090(18) . ?
C12 O1 1.2211(14) . ?
C13 C21 1.5316(18) . ?
C13 C14 1.5423(16) . ?
C14 O2 1.2117(15) . ?
C14 C15 1.4912(17) . ?
C15 C16 1.3952(17) . ?
C15 C20 1.4023(18) . ?
C16 C17 1.3915(19) . ?
C17 C18 1.385(2) . ?
C18 C19 1.387(2) . ?
C19 C20 1.384(2) . ?
C21 O3 1.2146(16) . ?
C21 C22 1.4897(18) . ?
C22 C27 1.397(2) . ?
C22 C23 1.400(2) . ?
C23 C24 1.390(2) . ?
C24 C25 1.374(3) . ?
C25 C26 1.381(3) . ?
C26 C27 1.388(2) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C2 C1 C6 120.94(13) . . ?
C3 C2 C1 119.46(13) . . ?
C4 C3 C2 121.03(14) . . ?
C4 C3 Cl1 119.70(12) . . ?
C2 C3 Cl1 119.24(12) . . ?
C3 C4 C5 119.11(14) . . ?
C4 C5 C6 121.29(13) . . ?
C5 C6 C1 118.11(13) . . ?
C5 C6 C7 120.26(11) . . ?
C1 C6 C7 121.59(11) . . ?
C8 C7 C6 112.93(10) . . ?
C8 C7 C13 111.78(10) . . ?
C6 C7 C13 110.03(10) . . ?
C9 C8 C12 108.29(11) . . ?
C9 C8 C7 130.78(11) . . ?
C12 C8 C7 120.92(10) . . ?
C8 C9 C10 113.79(10) . . ?
C9 C10 C11 103.81(10) . . ?
C12 C11 C10 105.27(10) . . ?
O1 C12 C8 125.24(11) . . ?
O1 C12 C11 126.23(11) . . ?
C8 C12 C11 108.53(10) . . ?
C21 C13 C7 110.46(10) . . ?
C21 C13 C14 107.60(10) . . ?
C7 C13 C14 108.78(9) . . ?
O2 C14 C15 120.72(11) . . ?
O2 C14 C13 118.31(11) . . ?
C15 C14 C13 120.96(10) . . ?
C16 C15 C20 119.18(12) . . ?
C16 C15 C14 123.42(11) . . ?
C20 C15 C14 117.40(11) . . ?
C17 C16 C15 120.13(12) . . ?
C18 C17 C16 120.24(13) . . ?
C17 C18 C19 119.96(13) . . ?
C20 C19 C18 120.34(14) . . ?
C19 C20 C15 120.15(13) . . ?
O3 C21 C22 121.18(13) . . ?
O3 C21 C13 120.26(12) . . ?
C22 C21 C13 118.55(11) . . ?
C27 C22 C23 119.34(13) . . ?
C27 C22 C21 118.28(13) . . ?
C23 C22 C21 122.33(13) . . ?
C24 C23 C22 119.75(15) . . ?
C25 C24 C23 120.32(17) . . ?
C24 C25 C26 120.49(15) . . ?
C25 C26 C27 120.12(17) . . ?
C26 C27 C22 119.95(17) . . ?

_diffrn_measured_fraction_theta_max 0.997
_diffrn_reflns_theta_full        31.31
_diffrn_measured_fraction_theta_full 0.997
_refine_diff_density_max         0.325
_refine_diff_density_min         -0.264
_refine_diff_density_rms         0.075

# Attachment 'chan43.cif'

data_chan43
_database_code_depnum_ccdc_archive 'CCDC 729201'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C21 H22 O2'
_chemical_formula_sum            'C21 H22 O2'
_chemical_formula_weight         306.39

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Triclinic
_symmetry_space_group_name_H-M   P-1

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   8.5087(4)
_cell_length_b                   10.7041(5)
_cell_length_c                   10.9088(5)
_cell_angle_alpha                112.218(3)
_cell_angle_beta                 93.624(3)
_cell_angle_gamma                107.362(3)
_cell_volume                     860.27(7)
_cell_formula_units_Z            2
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    3023
_cell_measurement_theta_min      0.00
_cell_measurement_theta_max      0.00

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.14
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.183
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             328
_exptl_absorpt_coefficient_mu    0.074
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.9809
_exptl_absorpt_correction_T_max  0.9897
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            12516
_diffrn_reflns_av_R_equivalents  0.0341
_diffrn_reflns_av_sigmaI/netI    0.0369
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         2.06
_diffrn_reflns_theta_max         25.02
_reflns_number_total             3027
_reflns_number_gt                2025
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[\s^2^(Fo^2^)+(0.0752P)^2^+0.2217P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         3027
_refine_ls_number_parameters     211
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0848
_refine_ls_R_factor_gt           0.0512
_refine_ls_wR_factor_ref         0.1569
_refine_ls_wR_factor_gt          0.1295
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_restrained_S_all      1.043
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 0.8286(3) 1.0716(3) 0.9476(2) 0.0577(7) Uani 1 1 d . . .
H1 H 0.7782 0.9876 0.9587 0.069 Uiso 1 1 calc R . .
C2 C 0.9581(4) 1.1842(3) 1.0472(3) 0.0700(8) Uani 1 1 d . . .
H2 H 0.9937 1.1753 1.1249 0.084 Uiso 1 1 calc R . .
C3 C 1.0343(3) 1.3080(3) 1.0328(3) 0.0658(8) Uani 1 1 d . . .
H3 H 1.1219 1.3830 1.0999 0.079 Uiso 1 1 calc R . .
C4 C 0.9808(3) 1.3210(3) 0.9188(3) 0.0591(7) Uani 1 1 d . . .
H4 H 1.0321 1.4051 0.9081 0.071 Uiso 1 1 calc R . .
C5 C 0.8512(3) 1.2100(2) 0.8200(2) 0.0499(6) Uani 1 1 d . . .
H5 H 0.8150 1.2206 0.7434 0.060 Uiso 1 1 calc R . .
C6 C 0.7737(3) 1.0832(2) 0.8319(2) 0.0405(5) Uani 1 1 d . . .
C7 C 0.6331(3) 0.9623(2) 0.7176(2) 0.0392(5) Uani 1 1 d . . .
H7 H 0.6696 0.9600 0.6336 0.047 Uiso 1 1 calc R . .
C8 C 0.6074(3) 0.8141(2) 0.7138(2) 0.0376(5) Uani 1 1 d . . .
C9 C 0.7002(3) 0.7342(2) 0.6428(2) 0.0423(5) Uani 1 1 d . . .
H9 H 0.7751 0.7729 0.5972 0.051 Uiso 1 1 calc R . .
C10 C 0.6864(3) 0.5998(2) 0.6369(2) 0.0429(6) Uani 1 1 d . . .
C11 C 0.7929(3) 0.5194(3) 0.5613(3) 0.0636(7) Uani 1 1 d . . .
H11A H 0.8684 0.5778 0.5262 0.095 Uiso 1 1 calc R . .
H11B H 0.7218 0.4314 0.4879 0.095 Uiso 1 1 calc R . .
H11C H 0.8563 0.4977 0.6214 0.095 Uiso 1 1 calc R . .
C12 C 0.5721(3) 0.5427(2) 0.7046(2) 0.0461(6) Uani 1 1 d . . .
C13 C 0.4760(3) 0.6190(2) 0.7774(2) 0.0478(6) Uani 1 1 d . . .
C14 C 0.3517(4) 0.5533(3) 0.8464(3) 0.0768(9) Uani 1 1 d . . .
H14A H 0.2747 0.4619 0.7817 0.115 Uiso 1 1 calc R . .
H14B H 0.2907 0.6160 0.8856 0.115 Uiso 1 1 calc R . .
H14C H 0.4099 0.5400 0.9162 0.115 Uiso 1 1 calc R . .
C15 C 0.4961(3) 0.7537(2) 0.7807(2) 0.0452(6) Uani 1 1 d . . .
H15 H 0.4331 0.8052 0.8293 0.054 Uiso 1 1 calc R . .
C16 C 0.4712(3) 0.9944(2) 0.7143(2) 0.0392(5) Uani 1 1 d . . .
C17 C 0.3458(3) 0.9083(2) 0.5869(2) 0.0464(6) Uani 1 1 d . . .
C18 C 0.1779(3) 0.9269(4) 0.5859(3) 0.0786(9) Uani 1 1 d . . .
H18A H 0.1257 0.8997 0.4936 0.094 Uiso 1 1 calc R . .
H18B H 0.1063 0.8624 0.6189 0.094 Uiso 1 1 calc R . .
C19 C 0.1887(4) 1.0742(4) 0.6687(3) 0.0974(12) Uani 1 1 d . . .
H19A H 0.0760 1.0768 0.6712 0.117 Uiso 1 1 calc R . .
H19B H 0.2437 1.1361 0.6266 0.117 Uiso 1 1 calc R . .
C20 C 0.2833(4) 1.1321(3) 0.8106(3) 0.0672(8) Uani 1 1 d . . .
H20A H 0.3146 1.2361 0.8519 0.081 Uiso 1 1 calc R . .
H20B H 0.2108 1.0937 0.8626 0.081 Uiso 1 1 calc R . .
C21 C 0.4372(3) 1.0939(3) 0.8152(2) 0.0517(6) Uani 1 1 d . . .
H21 H 0.5166 1.1440 0.8955 0.062 Uiso 1 1 calc R . .
O1 O 0.5473(3) 0.41007(17) 0.70500(19) 0.0673(5) Uani 1 1 d . . .
H1A H 0.5950 0.3672 0.6497 0.101 Uiso 1 1 calc R . .
O2 O 0.3753(2) 0.82462(17) 0.48686(16) 0.0591(5) Uani 1 1 d . . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
C1 0.0632(16) 0.0495(14) 0.0544(15) 0.0213(12) -0.0042(13) 0.0152(13)
C2 0.0736(19) 0.0656(18) 0.0578(17) 0.0168(14) -0.0126(14) 0.0234(16)
C3 0.0484(15) 0.0547(16) 0.0687(18) 0.0036(14) -0.0010(13) 0.0148(13)
C4 0.0557(16) 0.0427(14) 0.0688(18) 0.0156(13) 0.0206(14) 0.0114(12)
C5 0.0544(15) 0.0430(13) 0.0521(14) 0.0190(12) 0.0143(12) 0.0171(12)
C6 0.0406(12) 0.0381(12) 0.0435(13) 0.0152(10) 0.0081(10) 0.0171(10)
C7 0.0432(13) 0.0388(12) 0.0371(12) 0.0158(10) 0.0090(10) 0.0161(10)
C8 0.0360(12) 0.0373(11) 0.0365(11) 0.0122(10) 0.0036(9) 0.0136(9)
C9 0.0364(12) 0.0430(12) 0.0442(12) 0.0162(10) 0.0066(10) 0.0123(10)
C10 0.0400(13) 0.0382(12) 0.0451(13) 0.0113(10) 0.0029(10) 0.0153(10)
C11 0.0665(18) 0.0548(15) 0.0743(18) 0.0224(14) 0.0239(14) 0.0316(13)
C12 0.0529(14) 0.0349(12) 0.0484(13) 0.0156(11) 0.0042(11) 0.0157(11)
C13 0.0495(14) 0.0430(13) 0.0524(14) 0.0215(11) 0.0141(11) 0.0155(11)
C14 0.090(2) 0.0626(18) 0.095(2) 0.0437(17) 0.0496(18) 0.0293(16)
C15 0.0482(14) 0.0429(13) 0.0471(13) 0.0172(11) 0.0146(11) 0.0205(11)
C16 0.0426(12) 0.0370(11) 0.0418(12) 0.0184(10) 0.0086(10) 0.0162(10)
C17 0.0504(14) 0.0464(13) 0.0472(14) 0.0232(12) 0.0069(11) 0.0190(11)
C18 0.0530(17) 0.115(3) 0.0637(18) 0.0286(18) 0.0056(14) 0.0369(17)
C19 0.084(2) 0.134(3) 0.093(2) 0.039(2) 0.0173(19) 0.075(2)
C20 0.0718(18) 0.0823(19) 0.0674(18) 0.0329(15) 0.0287(15) 0.0488(16)
C21 0.0590(16) 0.0543(14) 0.0459(13) 0.0192(12) 0.0122(11) 0.0272(12)
O1 0.0903(14) 0.0446(10) 0.0791(13) 0.0296(10) 0.0302(11) 0.0320(9)
O2 0.0714(12) 0.0525(10) 0.0452(10) 0.0099(8) 0.0004(8) 0.0263(9)

_geom_special_details            
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C1 C6 1.381(3) . ?
C1 C2 1.383(3) . ?
C2 C3 1.364(4) . ?
C3 C4 1.368(4) . ?
C4 C5 1.374(3) . ?
C5 C6 1.381(3) . ?
C6 C7 1.525(3) . ?
C7 C16 1.518(3) . ?
C7 C8 1.519(3) . ?
C8 C15 1.388(3) . ?
C8 C9 1.391(3) . ?
C9 C10 1.383(3) . ?
C10 C12 1.393(3) . ?
C10 C11 1.506(3) . ?
C12 O1 1.374(3) . ?
C12 C13 1.398(3) . ?
C13 C15 1.387(3) . ?
C13 C14 1.495(4) . ?
C16 C21 1.329(3) . ?
C16 C17 1.475(3) . ?
C17 O2 1.219(3) . ?
C17 C18 1.500(3) . ?
C18 C19 1.461(4) . ?
C19 C20 1.499(4) . ?
C20 C21 1.487(3) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C6 C1 C2 120.3(2) . . ?
C3 C2 C1 120.8(3) . . ?
C2 C3 C4 119.4(2) . . ?
C3 C4 C5 120.1(2) . . ?
C4 C5 C6 121.4(2) . . ?
C1 C6 C5 117.9(2) . . ?
C1 C6 C7 122.9(2) . . ?
C5 C6 C7 119.16(19) . . ?
C16 C7 C8 112.78(17) . . ?
C16 C7 C6 112.14(17) . . ?
C8 C7 C6 113.58(16) . . ?
C15 C8 C9 117.31(19) . . ?
C15 C8 C7 122.95(18) . . ?
C9 C8 C7 119.7(2) . . ?
C10 C9 C8 123.1(2) . . ?
C9 C10 C12 117.7(2) . . ?
C9 C10 C11 121.0(2) . . ?
C12 C10 C11 121.4(2) . . ?
O1 C12 C10 122.7(2) . . ?
O1 C12 C13 116.0(2) . . ?
C10 C12 C13 121.3(2) . . ?
C15 C13 C12 118.5(2) . . ?
C15 C13 C14 121.5(2) . . ?
C12 C13 C14 120.0(2) . . ?
C13 C15 C8 122.1(2) . . ?
C21 C16 C17 119.0(2) . . ?
C21 C16 C7 125.1(2) . . ?
C17 C16 C7 115.94(18) . . ?
O2 C17 C16 122.1(2) . . ?
O2 C17 C18 121.0(2) . . ?
C16 C17 C18 116.9(2) . . ?
C19 C18 C17 113.1(3) . . ?
C18 C19 C20 113.3(3) . . ?
C21 C20 C19 111.8(2) . . ?
C16 C21 C20 125.6(2) . . ?

_diffrn_measured_fraction_theta_max 0.997
_diffrn_reflns_theta_full        25.02
_diffrn_measured_fraction_theta_full 0.997
_refine_diff_density_max         0.517
_refine_diff_density_min         -0.275
_refine_diff_density_rms         0.041